Infrared multiphoton decomposition of highly excited <i>t</i>‐butyl chloride‐d<sub>9</sub>

McAlpine, Robert D.; McRae, Glenn; Goodale, J. W.

doi:10.1002/kin.550260203

Cited by 2 publications

(2 citation statements)

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“…To test our extended method, we have applied it to the MPD of CF 2 HCl. This molecule can be regarded as a medium-size one, 10 and it has been extensively studied, mainly because is a good candidate for deuterium and 13 C separation 24 and for its potential role in atmospheric chemistry. 25 Because of its relatively simple chemistry, CF 2 HCl has often been chosen as a model molecule in studies of the basic properties of multiphoton dissociation.…”

Section: Resultsmentioning

confidence: 99%

“…From the magnitude and sign of the model parameters, h i j , one may infer the different contributions to the dissociation yield coming from the direct pressure-independent process ( h 10 ) and from the mechanisms induced by homogeneous and heterogenous collisions ( h 20 , h 11 , and higher order parameters). McRae et al have been able to find h i j parameters, only dependent on fluence, for a number of molecules, ,,,− working at pressure values where there is a rather high number of collisions during the time of the laser pulse.…”

Section: Analysis Methodsmentioning

confidence: 99%

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Collisionally Induced Bottleneck Weakening in IR Multiphoton Dissociation

Torresano

Santos

1996

J. Phys. Chem.

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An extension of the method of McRae et al. is proposed to quantify the contribution of the distinct collisional processes to the total yield obtained in infrared multiphoton dissociation experiments. The extension consists of the introduction of a substrate pressure dependence in the parameter representing one homogeneous collision. This allows the application of the method at a pressure where the collision time is of the order of the temporal width of the laser pulse and the discrimination between the different processes associated in a given collisional sequence. We have tested the reliability of this extended method by applying it to the multiphoton dissociation of CF 2 HCl, where the dependence of the dissociation yield on initial pressure and laser fluence has been investigated. We have shown that the homogeneous collisions occurring during the laser pulse may play a fundamental role in the weakening of the bottleneck absorption effects. It has been also suggested that fluence is the main excitation parameter for fixing the pressure interval along which dissociation can be regarded as collisionless.

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Section: Resultsmentioning

confidence: 99%